Hydrogeochemistry of porphyry related solutes in ground and surface waters; an example from the Casino Cu-Au-Mo deposit, Yukon, Canada

The Casino Cu-Au-Mo deposit is one of the largest and highest-grade porphyries of its kind in Canada, residing in an unglaciated region of west central Yukon. A batch of 22 stream water samples and eight groundwater samples were collected proximal to the deposit for the purpose of identifying the most diagnostic trace element and isotopic pathfinders associated with the hydrothermal mineralization, as well as establishing natural hydrogeochemical baselines for the area. Water chemistry around this deposit was investigated because: (i) the deposit has not yet been disturbed by mining; (ii) the deposit was known to have metal-rich waters in local streams; and (iii) the deposit has atypically preserved ore zones. Surface and ground waters around the Casino deposit are anomalous with respect to Cd (up to 5.4 µg/L), Co (up to 64 µg/L), Cu (up to 1657 µg/L), Mo (up to 25 µg/L), As (up to 17 µg/L), Re (up to 0.7 µg/L), and Zn (up to 354 µg/L) concentrations. Sulfur and Sr isotopes are consistent with proximal waters interacting with the Casino rocks and mineralization; a sulfide-rich bedrock sample from the deposit has δ34S = -1.2 ‰ and proximal groundwaters are only slightly heavier (-0.3 to 3.1 ‰). These geochemical and isotopic results indicate interaction and dispersion of porphyry related solutes in ground and surface waters and point to suitability of hydrogeochemistry as a medium for mineral exploration for porphyry-style mineralization in the Yukon, and elsewhere in Canada.Supplementary material: The physicochemical, major, trace, and isotopic data of stream and groundwaters used in this manuscript is publicly available as an Open File Report (OF 8823) from the Geological Survey of Canada.Thematic collection: This article is part of the Hydrochemistry related to exploration and environmental issues collection available at: https://www.lyellcollection.org/cc/hydrochemistry-related-to-exploration-and-environmental-issues

Tellus regional stream water geochemistry: environmental and mineral exploration applications

Regional stream water geochemistry acquired as part of the Tellus programme in Ireland has been analysed to assess its potential for application to environmental assessment and mineral exploration. Interpolated geochemical maps and multivariate statistical analysis, including principal component analysis and random forest classification, demonstrate broad geogenic control of stream water chemistry, with both bedrock and subsoil contributing to the patterns observed. Surface water regulations set Environmental Quality Standard values for individual Priority Substances and Specific Pollutants that may depend on background concentrations and/or water hardness. The high resolution of Tellus stream water data and their location on low-order streams have allowed estimation of background concentrations and water hardness in the survey area, with significant implications for water monitoring programmes. Anthropogenic inputs to stream water in the survey area come mainly from agricultural sources and Tellus data suggest few catchments are unaffected. Comparison of Tellus stream water geochemistry with stream sediment and topsoil geochemistry suggest that stream water geochemistry has strong potential for use in mineral exploration, with the same base metal and gold pathfinder anomalies apparent in all three data sets. Cluster analysis indicates that base metals in stream water are associated with organic matter but statistical analysis may be employed to distinguish mineralization-related signatures.Supplementary material: Comparison of cation/anion associations using Piper plots and principal component analysis is available at https://doi.org/10.6084/m9.figshare.c.5683094Thematic collection: This article is part of the Hydrochemistry related to exploration and environmental issues collection available at: https://www.lyellcollection.org/cc/hydrochemistry-related-to-exploration-and-environmental-issues

GEMAS: Adaptation of weathering indices for European agricultural soil derived from carbonate parent materials

Carbonate rocks are very soluble and export elements in dissolved form, and precipitation of secondary phases can occur at a large scale. They leave a strong chemical signature in soil that can be quantified and classified by geochemical indices, which are useful for evaluating chemical weathering trends (e.g., the Chemical Index of Alteration CIA or the Mafic Index of Alteration MIA). Due to contrasting chemical compositions and high Ca content, a special adaptation of classical weathering indices is necessary to interpret weathering trends in carbonate-derived soil. In fact, this adaptation seems to be a good tool for distinguishing weathering grades of source rock types at the continental-scale, and allows a more robust interpretation of soil parent material weathering grade and its impact on the current chemical composition of soil. Increasing degree of weathering results in Al enrichment and Mg loss in addition to Fe loss and Si enrichment, leaching of mobile cations such as Ca and Na and precipitation of Fe-oxides and hydroxides. Relation between soil weathering status and its spatial distribution in Europe provides important information on the role played by climate and terrain. Geographical distribution of soil chemistry contributes to a better understanding of soil nutritional status, element enrichment, degradation mechanisms, desertification, soil erosion and contamination.

Overview of surficial geochemistry and indicator mineral surveys and case studies from the Geological Survey of Canada's GEM Program

The Geological Survey of Canada carried out reconnaissance-scale to deposit-scale geochemical and indicator-mineral surveys and case studies across northern Canada between 2008 and 2020 as part of its Geo-mapping for Energy and Minerals (GEM) program. In these studies, surficial geochemistry was used to determine the concentrations of up to 65 elements in various sample media including lake sediment, lake water, stream sediment, stream water, or till samples across approximately 1 000 000 km2 of northern Canada. As part of these surficial geochemistry surveys, indicator mineral methods were also used in regional-scale and deposit-scale stream sediment and till surveys. Through this program, areas with anomalous concentrations of elements and/or indicator minerals that are indicative of bedrock mineralization were identified, new mineral exploration models and protocols were developed, a new generation of geoscientists was trained, and geoscience knowledge was transferred to northern communities. Regional- and deposit-scale studies demonstrated how transport data (till geochemistry, indicator mineral abundance) and ice-flow indicator data can be used together to identify and understand complex ice flow and glacial transport. Detailed studies at the Izok Lake Zn-Cu-Pb-Ag VMS, Nunavut, the Pine Point carbonate-hosted Pb-Zn in the Northwest Territories, the Strange Lake REE deposit in Quebec and Labrador as well as U-Cu-Fe-F and Cu-Ag-Au-Au IOCG deposits in the Great Bear magmatic zone, Northwest Territories demonstrate new suites of indicator minerals that can now be used in future reconnaissance- and regional-scale stream sediment and till surveys across Canada.

Fluids sources in basement-hosted unconformity-uranium ore systems: tourmaline chemistry and boron isotopes from the Patterson Lake corridor deposits, Canada

The Patterson Lake corridor is a new uranium district located on the southwestern margin of the Athabasca Basin. Known resources extend almost one kilometer below the unconformity in graphite- and sulfide-bearing shear zones within highly altered metamorphic rocks. Despite different host rocks and greater depths below the unconformity, alteration assemblages (chlorite, illite, kaolinite, tourmaline and hematite), ore grades and textures are typical of unconformity-related deposits. This alteration includes at least three generations of Mg-rich tourmaline (magnesio-foitite). The boron isotopic composition of magnesio-foitite varies with generation: the earliest generation only observed in shallow samples from the Triple R deposit (Tur 1) contain the heaviest isotopic signature (δ11B ≈ +26 to +19 ‰), whereas subsequent generations (Tur 2, Tur 3) yield lighter and more homogeneous isotopic signatures (δ11B ≈ +17.5 to +19.9 ‰). These results are consistent with precipitation from low temperature, NaCl- and CaCl2-rich brine(s) derived from an isotopically heavy boron source (e.g. evaporated seawater) that interacted with tourmaline and silicates in the basement rocks and/or fluids derived from depth (with low δ11B values). The lower δ11B values in paragenetically later magnesio-foitite reflect greater contributions of basement-derived boron over time whereas minor compositional variations reflect local metal sources (e.g. Cr, V, Ti) and evolving fluid chemistry (decreasing Na and Ca, increasing Mg) over time. The δ11B and chemical variation in magnesio-foitite over time reinforce the strong interactions with basement rocks in these systems while supporting incursion of basinal brines well below the unconformity contact.Thematic collection: This article is part of the Uranium Fluid Pathways collection available at: https://www.lyellcollection.org/cc/uranium-fluid-pathwaysSupplementary material:https://doi.org/10.6084/m9.figshare.c.5727555

Small-scale field evaluation of geochemical blending of waste rock to mitigate acid rock drainage potential

Blending of potentially acid generating (PAG) waste rock with non-PAG waste rock to create a rock mixture which performs as non-PAG is a possible approach to permanent prevention of acid rock drainage (ARD) for PAG waste rock. In 2012, a field weathering study using 300 kg samples was implemented at Teck Coal's Quintette Project located in northeastern British Columbia, Canada to test the prevention of acid generation in the PAG waste rock by dissolved carbonate leached from overlying non-PAG waste rock and direct neutralization of acidic water from PAG waste rock by contact with non-PAG waste rock.After eight years of monitoring the experiments, the layered non-PAG on PAG barrels provided proof-of-concept that as the thickness of the PAG layer increases relative to the thickness of the non-PAG layers, acidic waters are more likely to be produced. The PAG on non-PAG layering has resulted in non-acidic water and no indications of metal leaching despite accelerated oxidation in the PAG layer shown by sulphate loadings. The study has demonstrated that the scale of heterogeneity of PAG and non-PAG materials is a critical consideration for providing certainty that rock blends designed to be non-PAG will perform as non-PAG in perpetuity. This is contrary to the standard paradigm in which an excess of acid-consuming minerals is often considered sufficient alone to ensure ARD is not produced.

Geochemical evaluation of the in-situ regolith of Madengi hills of Dodoma, Tanzania. Implication on bedrock mapping and delineating gold mineralization target

Successful gold exploration projects depend on a piece of clear information on the association between gold, trace elements, and mineralization controlling factors. The use of soil geochemistry has been an important tool in pinpointing exploration targets during the early stage of exploration. This study aimed to establish the gold distribution, the elemental association between gold and its pathfinder elements such as Cu, Zn, Ag, Ni, Co, Mn, Fe, Cd, V, Cr, Ti, Sc, In, and Se and identify lithologies contributing to the overlying residual soils. From cluster analysis, a high similarity level of 53.93% has been shown with Ag, Cd, and Se at a distance level of 0.92. Au and Se have a similarity level of 65.87% and a distance level of 0.68, hence is proposed to be the most promising pathfinder element. PCA, FA, and the Pearson's correlation matrix of transformed data of V, Cu, Ni, Fe, Mn, Cr, and Co and a stronger correlation between Pb and U, Th, Na, K, Sn, Y, Ta and Be shows that source gold mineralization might be associated with both hornblende gneisses interlayered with quartzite, tonalite, and tonalitic orthogneiss. From the contour map and gridded map of Au and its pathfinder elements, it has been noted that their anomalies and target generated are localized in the Northern part of the area. The targets trend ESE to WNW nearly parallel to the shear zones as a controlling factor of Au mineralization emplacement.Supplementary material:https://doi.org/10.6084/m9.figshare.c.5721965

Suitability of surficial media for Ni-Cu-PGE exploration in an established mining camp: a case study from the South Range of the Sudbury Igneous Complex, Canada

A geochemical study over the southwestern part of the South Range of the Sudbury Igneous Complex (SIC) was completed to assess the suitability of surficial media (humus, B-horizon soil and C-horizon soil) for delineating geochemical anomalies associated with Ni-Cu-PGE mineralization. Another objective was to test whether Na pyrophosphate can eliminate the effects of anthropogenic contamination in humus. Results of this study suggest that the natural geochemical signature of humus is strongly overprinted by anthropogenic contamination. Despite no indication of underlying or nearby mineralization, metal concentrations in humus samples by aqua regia collected downwind from smelting operations are higher compared to background, including up to 13 times higher for Pt, 12 times higher for Cu and 9 times higher for Ni. The high anthropogenic background masks the geogenic signal such that it is only apparent in humus samples collected in the vicinity of known Ni-Cu-PGE deposits. Results of this study also demonstrate that anthropogenically-derived atmospheric fallout also influences the upper B-horizon soil; however, lower B-horizon soil (at > 20 cm depth) and C-horizon soil (both developed in till) are not affected. Glacial dispersal from Ni-Cu-PGE mineralization is apparent in C-horizon till samples analyzed in this study. Compared to the background concentrations, the unaffected C-horizon till samples collected immediately down-ice of the low-sulfide, high precious metal (LSHPM) Vermilion Cu-Ni-PGE deposit are enriched over 20 times in Pt (203 ppb), Au (81 ppm) and Cu (963 ppm), and over 30 times in Ni (1283 ppm).Supplementary material:https://doi.org/10.6084/m9.figshare.c.5691080

The effect of filtration size on the geochemistry of groundwater samples from a massive sulfide deposit at the Bathurst Mining Camp, New Brunswick, Canada

In hydrogeochemical studies, samples are commonly filtered to limit the fraction of analyte that is adsorbed or structurally bound to suspended particles, ensuring that only the dissolved fraction is analyzed, and thereby reducing analytical bias during measurement. The standard filter size that has been adopted is 0.45 μm, however, ultrafiltration can be used to remove colloidal particles two orders of magnitude smaller. In the following, we investigate the effect that standard (0.45 μm) and ultrafiltration (0.004 μm) have on the hydrogeochemistry of groundwaters from a volcanogenic massive sulfide (VMS) deposit at the Bathurst Mining Camp, New Brunswick, Canada. Groundwater samples were collected from six monitoring wells at the Nigadoo Mine tailings facility, and major and trace geochemistry were determined using a combination of inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and ion chromatography. Waters at the Nigadoo deposit are generally enriched in Ca and SO4, relative to other major cations and anions. Some element contents - including those associated with VMS deposits - differ depending on the filtration technique used (e.g., As, Fe, Pb, rare earth elements and yttrium [REY]), some are equally affected by both techniques (e.g., Cu, Ni, Zn), and some are unaffected by filtration (e.g., Ba, Ca, Mn, Cl-). Shale-normalized REY anomalies (CeSN/CeSN*, EuSN/EuSN*, and YSN/HoSN) and overall patterns can differ greatly (e.g., changing the sign of the anomaly) depending on the filtration technique used. We observe previously undocumented, and, at this time, unexplainable fractionation of Ho and Yb (non-redox sensitive REYs, unaffected by the tetrad effect) in unfiltered waters from the Nigadoo deposit. Differences in groundwater geochemistry induced by filtration technique can result in false positive and negative anomalies during environmental and exploration projects and must therefore be carefully considered. At the Nigadoo site, oxidation of sulfide minerals can occur, resulting in the formation of relatively unstable oxide minerals. Away from the tailings, where carbonate minerals are scarce and can no longer act as a pH buffer, the unstable oxide minerals break down and release metals and metalloids into the surrounding environment. The filtration methods used in this study can provide insight into where the specific metals and metalloids are hosted and how they are likely to behave under different redox conditions. Because VMS deposit pathfinder elements are enriched in unfiltered water, and differ by degree of filtration, geochemical analysis of the filtride material may also make an effective exploration tool.Thematic collection: This article is part of the Hydrochemistry related to exploration and environmental issues collection available at: https://www.lyellcollection.org/cc/hydrochemistry-related-to-exploration-and-environmental-issues

Geochemistry of natural acid rock drainage in the Mt. Evans area, Anaconda-Pintler Range, Montana, USA

This paper investigates natural acid rock drainage in two streams draining either side of Mount Evans, Montana. Bedrock consists of pyrrhotite-bearing schist intruded by granitic dikes and plutons of late Cretaceous to Tertiary age. The headwaters of both streams are moderately acidic (pH < 5.0) and carry elevated loads of dissolved sulfate, aluminum, and other trace metals (Cd, Co, Cu, Mn, Zn) as well as rare earth elements (REE). Copious aluminum precipitates inferred to be hydrobasaluminite coat boulders of both streams as pH rises > 5, with adsorption of copper and REE. Concentrations and loads of dissolved sulfate and trace elements are anomalously high in a small tributary that is sourced by meltwater from a rock glacier. The S-isotope composition of dissolved sulfate in both watersheds is similar to that of pyrrhotite in the meta-sediments, but not molybdenite in late porphyry dikes. Calculations of sulfate flux (i.e., sulfate load divided by surface area) indicate a relatively fast rate of sulfide oxidation in the study area, possibly due to exposure of fresh bedrock in the steep and recently glaciated field area. Overall, the geochemistry of the site suggests the possible presence of a metamorphosed sedimentary-exhalative (SEDEX) deposit, a possibility that is unlikely to be tested by drilling given the proximity of the site to a federal wilderness area. Thematic collection: This article is part of the Hydrochemistry related to exploration and environmental issues collection available at: https://www.lyellcollection.org/cc/hydrochemistry-related-to-exploration-and-environmental-issuesSupplementary material:https://doi.org/10.6084/m9.figshare.c.5649850